Glycine ethyl ester hydro­chloride

He, Y.-J.; Zou, P.; Wang, H.-Y.; Wu, H.; Xie, M.-H.

doi:10.1107/S1600536810028849

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2115

https://doi.org/10.1107/S1600536810028849

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Glycine ethyl ester hydrochloride

Yong-Jun He,^a Pei Zou,^a Hong-Yong Wang,^a Hao Wu ^a and Min-Hao Xie ^a ^*

^aJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
^*Correspondence e-mail: yongjunhe001@hotmail.com

(Received 12 May 2010; accepted 20 July 2010; online 24 July 2010)

In the crystal structure of the title compound, C₄H₁₀NO₂⁺·Cl⁻ (systematic name: 3-ethoxy-3-oxopropan-1-aminium chloride), there are strong intermolecular N—H⋯Cl, C—H⋯Cl and C—H⋯O hydrogen-bonding interactions between the free chloride anion and the organic cation, resulting in a two-dimensional supramolecular network in the ab plane.

Related literature

The title compound is an intermediate in the synthesis of dichlorovinylcyclopropane carboxylic acid, see: Xue (1995 ). For related structures, see: Taubald et al. (1984 ); Gainsford et al. (1986 ); Eduok et al. (1994 ).

Experimental

Crystal data

C₄H₁₀NO₂⁺·Cl⁻
M_r = 139.58
Monoclinic, P 2₁ /c
a = 8.965 (3) Å
b = 12.543 (4) Å
c = 5.972 (2) Å
β = 103.630 (5)°
V = 652.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 123 K
0.33 × 0.33 × 0.23 mm

Data collection

Rigaku SPIDER diffractometer
4996 measured reflections
1489 independent reflections
1294 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.064
S = 1.00
1489 reflections
87 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H0A⋯Cl1	0.904 (17)	2.300 (17)	3.1845 (16)	166.1 (12)
N1—H0B⋯Cl1ⁱ	0.906 (18)	2.386 (18)	3.1658 (16)	144.3 (15)
N1—H0C⋯Cl1	0.890 (19)	2.435 (19)	3.2566 (16)	153.7 (15)
C1—H1A⋯O2	0.99	2.47	2.9072 (18)	106
C3—H3B⋯Cl1ⁱⁱ	0.99	2.79	3.7529 (18)	164
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+1.

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810028849/bv2143sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028849/bv2143Isup2.hkl

checkCIF report

Comment top

The title compound, glycine ethyl ester hydrochloride is used in the preparation of dichlorovinylcyclopropane carboxylic acid, an important pesticide intermediate (Xue,1995).It is also used in the preparation of function material, the crystal structures of dichloro-bis(glycine ethyl ester)-palladium(II) (Taubald, et al., 1984),p,p-(µ₂-peroxo) -bis(tris(2-aminoethyl)-amine-N,N',N'',N''')-bis(ethylglycinate-N)-cobalt(II) tetraperchlorate (Gainsford et al., 1986),cis-β₂-((s,s)-chloro-(glycine ethyl ester-N)-(triethylenetetramine)-cobalt(III) dichloride trihydrate (Eduok et al., 1994) have been reported. The molecular structure of(I) is shown in Fig.1. The three crystallographically independent N—H moieties are engaged in highly directional N⁺—H···Cl^- hydrogen bonds with three symmetry-related Cl^- anions. These interactions promote the formation of a tape of C₄H₁₀NO₂ ⁺.Cl^- moieties running parallel to the c axis.

Related literature top

The title compound is an intermediate in the synthesis of dichlorovinylcyclopropane carboxylic acid, see: Xue (1995). For related structures, see: Taubald et al. (1984); Gainsford et al. (1986); Eduok et al. (1994).

Experimental top

Glycine ethyl ester hydrochloride (0.1 mmol, Sigma Aldrich at 99% purity) was dissolved methanol (20 ml) and gently heated under reflux for 1 h. After cooling the solution to ambient temperature, crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of the solvent after few days.

Structure description top

The title compound is an intermediate in the synthesis of dichlorovinylcyclopropane carboxylic acid, see: Xue (1995). For related structures, see: Taubald et al. (1984); Gainsford et al. (1986); Eduok et al. (1994).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.
	Fig. 2. A view of the packing arrangement of the title compound. Hydogran bonds are shown by dashed lines.

3-ethoxy-3-oxopropan-1-aminium chloride top

Crystal data top

C₄H₁₀NO₂⁺·Cl⁻	F(000) = 296
M_r = 139.58	D_x = 1.421 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 145(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.965 (3) Å	Cell parameters from 1964 reflections
b = 12.543 (4) Å	θ = 3.3–27.5°
c = 5.972 (2) Å	µ = 0.50 mm⁻¹
β = 103.630 (5)°	T = 123 K
V = 652.6 (4) Å³	Block, colorless
Z = 4	0.33 × 0.33 × 0.23 mm

Data collection top

Rigaku SPIDER diffractometer	1294 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.024
Graphite monochromator	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −10→11
4996 measured reflections	k = −16→11
1489 independent reflections	l = −7→7

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.031P)² + 0.160P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1489 reflections	Δρ_max = 0.40 e Å⁻³
87 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (3)

Crystal data top

C₄H₁₀NO₂⁺·Cl⁻	V = 652.6 (4) Å³
M_r = 139.58	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.965 (3) Å	µ = 0.50 mm⁻¹
b = 12.543 (4) Å	T = 123 K
c = 5.972 (2) Å	0.33 × 0.33 × 0.23 mm
β = 103.630 (5)°

Data collection top

Rigaku SPIDER diffractometer	1294 reflections with I > 2σ(I)
4996 measured reflections	R_int = 0.024
1489 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.40 e Å⁻³
1489 reflections	Δρ_min = −0.21 e Å⁻³
87 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	−0.00205 (3)	0.38254 (2)	0.24012 (5)	0.01640 (11)
O1	0.52878 (10)	0.38513 (7)	0.85715 (16)	0.0168 (2)
O2	0.34886 (10)	0.29775 (7)	0.59414 (15)	0.0171 (2)
N1	0.11868 (13)	0.36318 (9)	0.7845 (2)	0.0144 (2)
C2	0.38589 (14)	0.35635 (9)	0.7575 (2)	0.0132 (3)
C1	0.27318 (14)	0.40847 (10)	0.8745 (2)	0.0136 (3)
H1A	0.3056	0.3965	1.0429	0.016*
H1B	0.2709	0.4863	0.8461	0.016*
C3	0.64973 (15)	0.34018 (11)	0.7579 (2)	0.0184 (3)
H3A	0.6205	0.2672	0.7010	0.022*
H3B	0.7464	0.3354	0.8786	0.022*
C4	0.67496 (16)	0.40810 (11)	0.5624 (2)	0.0222 (3)
H4A	0.5809	0.4096	0.4392	0.027*
H4B	0.7589	0.3782	0.5029	0.027*
H4C	0.7015	0.4808	0.6179	0.027*
H0A	0.0807 (19)	0.3806 (11)	0.635 (3)	0.022 (4)*
H0B	0.054 (2)	0.3873 (13)	0.869 (3)	0.035 (5)*
H0C	0.1184 (19)	0.2925 (15)	0.797 (3)	0.033 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01827 (17)	0.01928 (19)	0.01196 (16)	0.00511 (12)	0.00419 (11)	0.00078 (11)
O1	0.0131 (4)	0.0206 (5)	0.0171 (5)	−0.0019 (4)	0.0045 (4)	−0.0039 (4)
O2	0.0163 (4)	0.0191 (5)	0.0157 (5)	−0.0003 (4)	0.0033 (4)	−0.0049 (4)
N1	0.0149 (5)	0.0166 (6)	0.0128 (5)	−0.0010 (4)	0.0055 (4)	−0.0022 (4)
C2	0.0150 (6)	0.0120 (6)	0.0131 (6)	−0.0006 (5)	0.0043 (5)	0.0027 (4)
C1	0.0136 (6)	0.0132 (6)	0.0141 (6)	−0.0010 (5)	0.0038 (5)	−0.0020 (5)
C3	0.0130 (6)	0.0224 (7)	0.0202 (7)	0.0013 (5)	0.0046 (5)	−0.0017 (5)
C4	0.0216 (7)	0.0228 (7)	0.0252 (7)	−0.0032 (5)	0.0115 (6)	−0.0029 (6)

Geometric parameters (Å, º) top

O1—C2	1.3290 (15)	C1—H1A	0.9900
O1—C3	1.4654 (16)	C1—H1B	0.9900
O2—C2	1.2040 (15)	C3—C4	1.505 (2)
N1—C1	1.4762 (16)	C3—H3A	0.9900
N1—H0A	0.902 (17)	C3—H3B	0.9900
N1—H0B	0.906 (19)	C4—H4A	0.9800
N1—H0C	0.890 (18)	C4—H4B	0.9800
C2—C1	1.5065 (18)	C4—H4C	0.9800

C2—O1—C3	116.20 (10)	C2—C1—H1B	109.7
C1—N1—H0A	111.7 (10)	H1A—C1—H1B	108.2
C1—N1—H0B	109.8 (12)	O1—C3—C4	110.89 (11)
H0A—N1—H0B	109.0 (16)	O1—C3—H3A	109.5
C1—N1—H0C	111.9 (11)	C4—C3—H3A	109.5
H0A—N1—H0C	108.6 (14)	O1—C3—H3B	109.5
H0B—N1—H0C	105.6 (15)	C4—C3—H3B	109.5
O2—C2—O1	125.54 (12)	H3A—C3—H3B	108.0
O2—C2—C1	123.62 (12)	C3—C4—H4A	109.5
O1—C2—C1	110.83 (11)	C3—C4—H4B	109.5
N1—C1—C2	109.79 (10)	H4A—C4—H4B	109.5
N1—C1—H1A	109.7	C3—C4—H4C	109.5
C2—C1—H1A	109.7	H4A—C4—H4C	109.5
N1—C1—H1B	109.7	H4B—C4—H4C	109.5

C3—O1—C2—O2	−0.45 (18)	O1—C2—C1—N1	−171.55 (10)
C3—O1—C2—C1	−179.62 (10)	C2—O1—C3—C4	86.87 (14)
O2—C2—C1—N1	9.27 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H0A···Cl1	0.904 (17)	2.300 (17)	3.1845 (16)	166.1 (12)
N1—H0B···Cl1ⁱ	0.906 (18)	2.386 (18)	3.1658 (16)	144.3 (15)
N1—H0C···Cl1	0.890 (19)	2.435 (19)	3.2566 (16)	153.7 (15)
C1—H1A···O2	0.99	2.47	2.9072 (18)	106
C3—H3B···Cl1ⁱⁱ	0.99	2.79	3.7529 (18)	164

Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula	C₄H₁₀NO₂⁺·Cl⁻
M_r	139.58
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	8.965 (3), 12.543 (4), 5.972 (2)
β (°)	103.630 (5)
V (Å³)	652.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.50
Crystal size (mm)	0.33 × 0.33 × 0.23

Data collection
Diffractometer	Rigaku SPIDER
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4996, 1489, 1294
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.064, 1.00
No. of reflections	1489
No. of parameters	87
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.21

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H0A···Cl1	0.904 (17)	2.300 (17)	3.1845 (16)	166.1 (12)
N1—H0B···Cl1ⁱ	0.906 (18)	2.386 (18)	3.1658 (16)	144.3 (15)
N1—H0C···Cl1	0.890 (19)	2.435 (19)	3.2566 (16)	153.7 (15)
C1—H1A···O2	0.9900	2.4700	2.9072 (18)	106.00
C3—H3B···Cl1ⁱⁱ	0.9900	2.7900	3.7529 (18)	164.00

Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+1.

Acknowledgements

This work was supported by the Science Foundation of the Health Department of Jiangsu Province (No. H200934).

References

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